화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.103, No.34, 7277-7286, 1999
Electron spin resonance and electron spin echo modulation studies of ion-exchanged NiH-SAPO-17 and NiH-SAPO-35 molecular sieves: Comparison with ion-exchanged NiH-SAPO-34 molecular sieve
Erionite-like silicoaluminophosphate molecular sieve SAPO-17 and levyne-like SAPO-35, in which Ni ions were incorporated via solid-state ion-exchange into known extraframework sites, have been studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM). The Ni ion reducibility, location, and interaction with several adsorbates have been investigated. Among these adsorbates, the interaction with nitric oxide was emphasized and compared to that of Ni ion with NO in the previously studied chabazite-like SAPO-34. Room-temperature adsorption of C2D4 on NiH-SAPO-17 after dehydration at 573 K, oxygen treatment at 823 K, evacuation, and subsequent hydrogen treatment at 573 K produces two Ni-ethylene complexes. Carbon monoxide adsorption gives rise to a Ni(I)-(CO)(n) complex with unresolved C-13 hyperfine lines. Following the kinetics of nitric oxide adsorption on NiH-SAPO-17 shows that initially, a Ni(I)(NO)(+) complex, a NO radical, and a new species which appears to be another NO species are generated. After a reaction time of 24 h, NO2 is observed. As the adsorption time further increases, NO: becomes stronger while Ni(I)-(NO)(+) decays, and after 5 days only NO2 remains. NO adsorption on NiH-SAPO-35 shows different features. Initially, two Ni(I)-(NO)(+) complexes along with a NO radical are seen. As the adsorption time increases, one of the Ni(I)-(NO)(+) complexes decreases in intensity while the other one increases, and after a few days only one Ni(I)-(NO)(+) complex remains. Simulation of the P-31 ESEM spectrum: supplemented by Al-27 modulation, suggests that, upon dehydration, Ni ions in NiH-SAPO-17 migrate from the erionite supercage to the smaller cancrinite cage. In dehydrated NiH-SAPO-34 and NiH-SAPO-35, Ni ions remain in the large chabazite and levyne cages, respectively. As a consequence, Ni(II) in NiH-SAPO-17 is less sensitive to reduction by hydrogen than it is in NiH-SAPO-34 and NiH-SAPO-35.